N-cyanoalkylanthranilamides as insecticides

ABSTRACT

Compounds of formula (I) wherein the substituents are as defined in claim  1,  and the agrochemically acceptable salts and all stereoisomers and tautomeric forms of the compounds of formula (I) can be used as agrochemical active ingredients and can be prepared in a manner known per se.

The present invention relates to novel anthranilamide derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling insects or representatives of the order Acarina.

Anthranilamide derivatives with insecticidal properties are known and described, for example, in WO 2006/040113 and WO 2006/055922. There have now been found novel anthranilamide derivatives with pesticidal properties, especially for the control of insects and members of the order Acarina. The novel compounds are characterised by a quaternary carbon atom which is part of the aliphatic (thio)amide side chain attached to the core aromatic ring and which carry an a-amino nitrile functionality and a cycloalkyl group.

The present invention accordingly relates to compounds of formula I

wherein

-   D is phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl; or phenyl,     2-pyridyl, 3-pyridyl or 4-pyridyl mono-, di- or trisubstituted by     C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, cyano,     C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,     C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl or     C₁-C₄haloalkylsulfonyl; or D is a group

-   R_(4a), R_(4b), R₁₀, R₁₇, and R₁₉ independently from each other, are     hydrogen, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen,     cyano, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₂-C₄alkoxycarbonyl,     C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl,     C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl or     C₁-C₄haloalkylsulfonyl; -   R_(5a), R₆, R₈, R₁₁, R₁₂, R₁₅, R₁₆ and R₁₈ independently from each     other, are C₁-C₆alkyl, or C₁-C₆alkyl mono-, di- or trisubstituted by     substituents independently selected from the group consisting of     halogen, cyano, nitro, hydroxy, C₁-C₄alkoxy, C₂-C₄alkoxycarbonyl,     C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,     C₁-C₄alkylamino, C₂-C₄dialkylamino and C₃-C₆cycloalkylamino; or are     phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl; or are phenyl, 2-pyridyl,     3-pyridyl or 4-pyridyl mono-, di- or trisubstituted by substituents     independently selected from the group consisting of C₁-C₆alkyl,     C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, cyano, C₁-C₄alkoxy,     C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,     C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl and     C₁-C₄haloalkylsulfonyl; -   R₇, R₉, R₁₃ and R₁₄ independently from each other, are hydrogen,     C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,     C₃-C₆alkynyl or C₃-C₆haloalkynyl; -   each R₁ independently is halogen, nitro, hydroxy, C₁-C₆alkyl,     C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl,     C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl,     C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,     C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, C₁-C₄alkylsulfinyl,     C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₄dialkylamino,     C₃-C₆cycloalkylamino, C₁-C₆alkyl-C₃-C₆cycloalkylamino,     C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl,     C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy,     C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy or     C₃-C₆trialkylsilyl, phenyl, benzyl or phenoxy, or phenyl, benzyl or     phenoxy mono-, di- or trisubstituted by halogen, cyano, nitro,     halogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,     C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl,     C₃-C₆halocycloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio,     C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,     C₁-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino,     C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl,     C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl,     C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy,     C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy or     C₃-C₆trialkylsilyl; -   n is 0, 1, 2 or 3; -   each of R₂ and R₃, which may be the same or different, represents     hydrogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₅cycloalkyl;     or C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₈cycloalkyl     substituted by one, two or three substituents independently selected     from the group consisting of halogen nitro, cyano, hydroxy,     C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio,     C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino,     C₂-C₄dialkylamino, C₃-C₆cycloalkylamino and     C₁-C₆alkyl-C₃-C₆cycloalkylamino; -   each of E₁ and E₂, which may be the same or different, represents     oxygen or sulfur; -   G is a group

and in particular

each of R₉₁ and R₉₂, which may be the same or different, have the meanings given for R₁;

-   R₄ is C₁-C₃alkyl or C₃-C₄cycloalkyl; or C₁-C₃alkyl or     C₃-C₄cycloalkyl substituted by one, two or three substituents     independently selected from the group consisting of halogen, cyano,     C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,     C₂-C₄alkoxycarbonyl and C₂-C₄haloalkoxycarbonyl; -   R₅ is C₃-C₄cycloalkyl or C₃-C₄cycloalkyl-C₁-C₃alkyl; or     C₃-C₄cycloalkyl or C₃-C₄cycloalkyl-C₁-C₃alkyl substituted by one,     two or three substituents independently selected from the group     consisting of halogen, cyano, C₁-C₃alkyl, C₃-C₄cycloalkyl,     C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₂-C₄alkoxycarbonyl     and C₂-C₄haloalkoxycarbonyl; -   and agronomically acceptable     salts/isomers/diastereomers/enantiomers/tautomers/N-oxides of those     compounds.

Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C₁-C₄alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C₁-C₄alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine. Where appropriate, the corresponding internal salts can furthermore be formed. Preferred within the scope of the invention are agrochemically advantageous salts; however, the invention also encompasses salts which have disadvantage for agrochemical use, for example salts which are toxic to bees or fish, and which are employed, for example, for the isolation or purification of free compounds of formula I or agrochemically utilizable salts thereof. Owing to the close relationship between the compounds of formula I in free form and in the form of their salts, for the purposes of the invention the free compounds of formula I or their salts hereinabove and hereinbelow are respectively to be understood as including, where appropriate, the corresponding salts or the free compounds of formula I. The same applies analogously to tautomers of compounds of formula I and salts thereof. In general, the free form is preferred in each case.

The alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl and their branched isomers. Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned. The alkenyl and alkynyl groups can be mono- or polyunsaturated.

Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichioroethyl; preferably trichloro-methyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Suitable haloalkenyl groups are alkenyl groups which are mono- or polysubstituted by halogen, halogen being fluorine, chlorine, bromine and iodine and in particular fluorine and chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en-1-yl. Among the alkenyl groups which are mono-, di- or trisubstituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.

Suitable haloalkynyl groups are, for example, alkynyl groups which are mono- or polysubstituted by halogen, halogen being bromine, iodine and in particular fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoro-propynyl and 4,4,4-trifluorobut-2-yn-1-yl. Among the alkynyl groups which are mono- or polysubstituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.

Alkoxy groups preferably have a preferred chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.

Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy. Alkylthio groups preferably have a chain length of from 1 to 6 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl. Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Examples of alkoxyalkoxy groups are: methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy or butoxybutoxy. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomeric butylamines. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino. Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms. Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl. The cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Phenyl, also as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, may be substituted. In this case, the substituents can be in ortho, meta and/or para position. The preferred substituent positions are the ortho and para positions to the ring attachment point.

E₁ and/or E₂ is preferably oxygen.

Preference is given to subgroups of compounds of formula I wherein

-   a) R₂ is hydrogen or C₁-C₄alkyl; and/or -   b) R₃ is hydrogen or C₁-C₄alkyl; and/or -   c) D is a group D₁.

A preferred subgroup of compounds of formula I is where G is the group G_(1a), therefore represented by the compounds of formula Ia

wherein

-   R₉₁ is preferably C₁-C₄alkyl or halogen, preferably chloro, bromo or     methyl; -   R₉₂ is preferably halogen, preferably fluoro, chloro or bromo; -   R₉₃ is preferably halogen, cyano, C₁-C₄haloalkyl, C₁-C₄alkoxy or     C₁-C₄haloalkoxy; and -   E₂, R₄ and R₅ have the meanings given under formula I.

Special emphasis should also be given to compounds of formula I wherein

-   d) R₄ is C₁-C₃alkyl, preferably methyl; and/or -   e) R₅ is C₃-C₄cycloalkyl.

“Me” represents the methyl group.

Further preferred embodiments of the present invention are the embodiments E1 to E8, which are defined as compounds of formula I which are represented by one formula selected from the group consisting of the formulae T1 to T8 as described below, wherein in formulae T1 to T8

-   R₉₁ is preferably C₁-C₄alkyl or halogen, preferably chloro, bromo or     methyl; -   R₉₂ is preferably halogen, preferably fluoro, chloro or bromo; -   R₉₃ is preferably halogen, cyano, C₁-C₄haloalkyl, C₁-C₄alkoxy or     C₁-C₄haloalkoxy; and -   P is nitrogen or methine, preferably nitrogen.

For example, embodiment E1 is represented by the compounds of formula T1

wherein

-   R₉₁ is preferably C₁-C₄alkyl or halogen, preferably chloro, bromo or     methyl; -   R₉₂ is preferably halogen, preferably fluoro, chloro or bromo; -   R₉₃ is preferably halogen, cyano, C₁-C₄haloalkyl, C₁-C₄alkoxy or     C₁-C₄haloalkoxy; and -   P is nitrogen or methine, preferably nitrogen.

Embodiments E2 to E8 are defined accordingly.

The process according to the invention for preparing compounds of the formula I is carried out analogously to known processes, for example those described in WO 01/70671, WO 03/016284, WO 03/015518 and WO 04/033468.

The process for the preparation of a compound of the formula I or, where appropriate, a tautomer thereof, in each case in free form or in salt form, comprises, for example,

-   a) to prepare a compound of formula I, in which R₂ is hydrogen and     E₁ and E₂ are oxygen, or, where appropriate, a tautomer and/or salt     thereof, by reacting a compound of formula II

in which G, R₁, n, and D have the meanings given for formula I, or, where appropriate, a tautomer and/or salt thereof with a compound of formula III

in which R₃, R₄ and R₅ have the meanings given for the formula I, or, where appropriate, with a tautomer and/or salt thereof or,

-   b) to prepare a compound of formula I, or, where appropriate, a     tautomer and/or salt thereof, reacting a compound of formula IV

in which G, R₁, R₂, n, E₁, E₂ and D have the meanings given for the formula I; and X₁ is a leaving group,or, where appropriate, a tautomer and/or salt thereof with a compound of formula III

in which R₃, R₄ and R₅ have the meanings given for formula I, or, where appropriate, with a tautomer and/or salt thereof or,

-   c) to prepare a compound of formula I, or, where appropriate, a     tautomer and/or salt thereof, by reacting a compound of formula V

in which G, n, R₁, R₂, R₃, E₂, R₄ and R₅ have the meanings given for formula I, or, where appropriate, a tautomer and/or salt thereof with a compound of formula VI

X₂C(=E₁)D   (VI),

in which E₁ and D have the meanings given for formula I; and X₂ is a leaving group, or, where appropriate, with a tautomer and/or salt thereof and/or converting a compound of formula I or, where appropriate, a tautomer thereof, in each case in free form or in salt form, into another compound of formula I or, where appropriate, a tautomer thereof, separating an isomer mixture, which can be obtained in accordance with the process, and isolating the desired isomer and/or converting a free compound of formula I or, where appropriate, a tautomer thereof into a salt or a salt of a compound of formula I or, where appropriate, a tautomer thereof into the free compound of formula I or, where appropriate, a tautomer thereof or into another salt.

The compounds of formula II are described in WO 04/111030.The compounds of formula V are novel and especially developed for the preparation of the compounds of formula I and constitute therefore a further embodiment of the present invention. The preferences for the substituents of formula I mentioned above are also valid for the compounds of formula V.

In especially preferred compounds of formula V

-   R₁ is C₁-C₄alkyl, halogen, C₁-C₅haloalkyl, nitro, C₁-C₄alkoxy,     C₁-C₄-haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl,     C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl or     C₁-C₄haloalkylsulfonyl; -   n is 1, 2 or 3; -   R₂ and R₃ are hydrogen or methyl; -   E₂, R₄ and R₅ have the meanings given under formula I.

Special emphasis should also be given to a subgroup of compounds of formula V represented by the compounds of formula Va

wherein

-   R₉₁ is C₁-C₄alkyl or halogen, preferably chloro, bromo or methyl; -   R₉₂ is halogen, preferably fluoro, chloro or bromo; and -   E₂, R₄ and R₅ have the meanings given under formula I.

TABLE D Preferred compounds of formula V represented by formula Va where E₂ is oxygen: (Va)

“cyclo-C3” is cyclopropyl and ”cyclo-C4⇄ is cyclobutyl: Comp. No. R₉₁ R₉₂ R₄ R₅ D1 Me F iso-propyl Cyclo-C3 D2 Me F CH₃ Cyclo-C3 D3 Me F iso-propyl

D4 Me F CH₃

D5 Me F CH₃ Cyclo-C4 D6 Me F iso-propyl —CH₂-cyclo-C3 D7 Me F CH₃ —CH₂-cyclo-C3 D8 Me Cl iso-propyl Cyclo-C3 D9 Me Cl CH₃ Cyclo-C3 D10 Me Cl CH₂CH₃ Cyclo-C3 D11 Me Cl CH₂OCH₃ Cyclo-C3 D12 Me Cl Cyclo-C3 Cyclo-C3 D13 Me Cl iso-propyl

D14 Me Cl CH₃

D15 Me Cl CH₃

D16 Me Cl iso-propyl Cyclo-C4 D17 Me Cl CH₃ Cyclo-C4 D18 Me Cl iso-propyl —CH₂-cyclo-C3 D19 Me Cl CH₃ —CH₂-cyclo-C3 D20 Me Br iso-propyl Cyclo-C3 D21 Me Br CH₃ Cyclo-C3 D22 Me Br CH₂CH₃ Cyclo-C3 D23 Me Br CH₂OCH₃ Cyclo-C3 D24 Me Br Cyclo-C3 Cyclo-C3 D25 Me Br iso-propyl

D26 Me Br CH₃

D27 Me Br CH₃

D28 Me Br iso-propyl Cyclo-C4 D29 Me Br CH₃ Cyclo-C4 D30 Me Br iso-propyl —CH₂-cyclo-C3 D31 Me Br CH₃ —CH₂-cyclo-C3 D32 Cl F iso-propyl Cyclo-C3 D33 Cl F CH₃ Cyclo-C3 D34 Cl F iso-propyl

D35 Cl F CH₃

D36 Cl F CH₃ Cyclo-C4 D37 Cl F iso-propyl —CH₂-cyclo-C3 D38 Cl F CH₃ —CH₂-cyclo-C3 D39 Cl Cl iso-propyl Cyclo-C3 D40 Cl Cl CH₃ Cyclo-C3 D41 Cl Cl CH₂CH₃ Cyclo-C3 D42 Cl Cl CH₂OCH₃ Cyclo-C3 D43 Cl Cl Cyclo-C3 Cyclo-C3 D44 Cl Cl iso-propyl

D45 Cl Cl CH₃

D46 Cl Cl CH₃

D47 Cl Cl iso-propyl Cyclo-C4 D48 Cl Cl CH₃ Cyclo-C4 D49 Cl Cl iso-propyl —CH₂-cyclo-C3 D50 Cl Cl CH₃ —CH₂-cyclo-C3 D51 Cl Br iso-propyl Cyclo-C3 D52 Cl Br CH₃ Cyclo-C3 D53 Cl Br CH₂CH₃ Cyclo-C3 D54 Cl Br CH₂OCH₃ Cyclo-C3 D55 Cl Br Cyclo-C3 Cyclo-C3 D56 Cl Br iso-propyl

D57 Cl Br CH₃

D58 Cl Br CH₃

D59 Cl Br iso-propyl Cyclo-C4 D60 Cl Br CH₃ Cyclo-C4 D61 Cl Br iso-propyl —CH₂-cyclo-C3 D62 Cl Br CH₃ —CH₂-cyclo-C3 D63 Br F iso-propyl Cyclo-C3 D64 Br F CH₃ Cyclo-C3 D65 Br F iso-propyl

D66 Br F CH₃

D67 Br F CH₃ Cyclo-C4 D68 Br F iso-propyl —CH₂-cyclo-C3 D69 Br F CH₃ —CH₂-cyclo-C3 D70 Br Cl iso-propyl Cyclo-C3 D71 Br Cl CH₃ Cyclo-C3 D72 Br Cl iso-propyl

D73 Br Cl CH₃

D74 Br Cl CH₃ Cyclo-C4 D75 Br Cl iso-propyl —CH₂-cyclo-C3 D76 Br Cl CH₃ —CH₂-cyclo-C3 D77 Br Br iso-propyl Cyclo-C3 D78 Br Br CH₃ Cyclo-C3 D79 Br Br iso-propyl

D80 Br Br CH₃

D81 Br Br CH₃ Cyclo-C4 D82 Br Br iso-propyl —CH₂-cyclo-C3 D83 Br Br CH₃ —CH₂-cyclo-C3

TABLE G Preferred compounds of formula V represented by formula Va where E₂ is sulfur listing compounds G1 to G83 wherein R₉₁, R₉₂, R₄ and R₅ have the meanings given in Table D lines D1 to D83. Physical data for compounds of formula Va according to Tables D and G: Compound No. melting point ¹H-NMR D9, template Va 156-158° C. CDCl₃: 7.17 (d, 1H), 7.14 (d, 1H), 6.19 (s, 1H), 5.5-3.0 (br s, 2H), 2.15 (s, 3H), 1.86 (s, 3H), 1.39-1.30 (m, 1H), 0.83-0.73 (m, 4H) D17, template Va 128-130° C.

Compounds of formula Vc, a subgroup of compounds of formula V where R₂ is hydrogen, can be prepared for example in analogy to methods described in WO2001/070671.

The compounds of formula Vc can also be prepared by reacting a compound of formula XI with a compound of formula III in the presence of a base and an inert solvent

in which G, n, R₁, R₃, E₂, R₄, and R₅ have the meanings given in formula I; and X₁ is a leaving group (for example chlorine, bromine), or, where appropriate, a tautomer and/or salt thereof.

Suitable bases are for example N(C₂H₅)₃, DBU, DBN or imidazole. Preferred solvents are tetrahydrofurane, dioxane, glyme, ethyl acetate or toluene. The reaction is carried out at temperatures of from 0° C. to 100° C., preferably at +15° C. to +30° C. in particular at ambient temperature.

Amides of formula VNaNc where E₂ is oxygen are readily converted to thioamides of formula VNaNc where E₂ is sulfur by using commercially available thio transfer reagents such as phosphorus pentasulfide and Lawesson's reagent, for example in analogy to X. Fontrodona et al., Synthesis, 2001, (13), 2021-27.

Compounds of formula XI, in particular those compounds of formula XI where X, is chlorine, can be prepared for example in analogy to J. Garin et al., Tetrahedron Letters, 1991, 32, 3263-64.

Compounds of formula III are either known in the literature or can be prepared in analogy according to known methods. In particular compounds of formula IIla, a subgroup of compounds of formula III where R₃ is hydrogen, can be prepared for example as described in Tetrahedron 1999, 55, 7625-7644 by means of the Strecker reaction, or in further analogy according to known methods.

What has been said above for tautomers and/or salts of compounds of formula I applies analogously to starting materials mentioned hereinabove and hereinbelow with regard to the tautomers and/or salts thereof.

The reactions described hereinabove and hereinbelow are carried out in a manner known per se, for example in the absence or, normally, in the presence of a suitable solvent or diluent or of a mixture of these, the process being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of from approximately −80° C. to the boiling point of the reaction mixture, preferably from approximately −20° C. to approximately +150° C., and, if required, in a sealed vessel, under reduced, normal or elevated pressure, in an inert gas atmosphere and/or under anhydrous conditions. Especially advantageous reaction conditions can be seen from the examples.

Unless otherwise specified, the starting materials mentioned hereinabove and hereinbelow, which are used for the preparation of the compounds of formula I or, where appropriate, the tautomers thereof, in each case in free form or in salt form, are known or can be prepared by methods known per se, for example in accordance with the information given below. The reactants can be reacted in the presence of a base. Examples of suitable bases for facilitating the detachment of HX₂ are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

The reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range from approximately −80° C. to approximately +140° C., preferably from approximately −30° C. to approximately +100° C., in many cases in the range between room temperature and approximately +80° C.

A compound of formula I can be converted in a manner known per se into another compound I by replacing one or more substituents of the starting compound of formula I in the customary manner by (an)other substituent(s) according to the invention.

Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step.

Salts of compounds of formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in the customary manner into the free compounds of formula I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds of formula I, which have salt-forming properties can be obtained in free form or in the form of salts.

The compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.

Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.

It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.

The compounds according to the invention and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.

The compounds according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate, a good activity corresponding to a destruction rate (mortality) of at least 50 to 60%.

Examples of the abovementioned animal pests are:

-   from the order Acarina, for example, -   Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp.,     Argas spp., Boophi-lus spp., Brevipalpus spp., Bryobia praetiosa,     Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,     Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp.,     Olygonychus pratensis, Ornithodoros spp., Panonychus spp.,     Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp.,     Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus     spp. and Tetranychus spp.; -   from the order Anoplura, for example, -   Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp.     and Phylloxera spp.; -   from the order Coleoptera, for example, -   Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema     tibialis, Cosmopolites spp., Curculio spp., Dermestes spp.,     Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa     decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus     spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes     spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga     spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; -   from the order Diptera, for example, -   Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora     erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp.,     Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp.,     Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp.,     Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp.,     Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami,     Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp.,     Tabanus spp., Tannia spp. and Tipula spp.; -   from the order Heteroptera, for example, -   Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp.,     Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp.,     Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and     Triatoma spp.; -   from the order Homoptera, for example, -   Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp.,     Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster     spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus     hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,     Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,     Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp.,     Parlatoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis     spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica,     Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,     Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes     vaporariorum, Trioza erytreae and Unaspis citri; -   from the order Hymenoptera, for example, Acromyrmex, Atta spp.,     Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma,     Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp.,     Solenopsis spp. and Vespa spp.; -   from the order lsoptera, for example, -   Reticulitermes spp.; -   from the order Lepidoptera, for example, -   Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama     argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,     Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella,     Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia     ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,     Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta,     Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp.,     Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp.,     Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp.,     Hellula undalis, Hyphantria cunea, Keiferia lycopersicella,     Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria     spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca     sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis     spp., Panolis flammea, Pectinophora gossypiela, Phthorimaea     operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays     spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera     spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp.,     Trichoplusia ni and Yponomeuta spp.; -   from the order Mallophaga, for example, -   Damalinea spp. and Trichodectes spp.; -   from the order Orthoptera, for example, -   Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,     Locusta spp., Periplaneta spp. and Schistocerca spp.; -   from the order Psocoptera, for example, -   Liposcelis spp.; -   from the order Siphonaptera, for example, -   Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; -   from the order Thysanoptera, for example, -   Frankliniella spp., Hercinothrips spp., Scirtothrips aurantii,     Taeniothrips spp., Thrips palmi and Thrips tabaci; and -   from the order Thysanura, for example, -   Lepisma saccharina.

The active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family, latex plants and ornamentals.

The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops. The active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).

The term “crops” is to be understood as including also crops that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.

The term “crops” is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood by δ-endotoxins, for example CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidal proteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated CryIA(b), are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CryIIIA055, a cathepsin-D-recognition sequence is inserted into a CryIIIA toxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CryIIIB(b1) toxin); YieldGard Plus® (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CryIA(c) toxin); Bollgard I® (cotton variety that expresses a CryIA(c) toxin); Bollgard II® (cotton variety that expresses a CryIA(c) and a CryIIA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CryIIIA toxin); Nature-Gard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

-   1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31     790 St. Sauveur, France, registration number C/FR/96/05/10.     Genetically modified Zea mays which has been rendered resistant to     attack by the European corn borer (Ostrinia nubilalis and Sesamia     nonagrioides) by transgenic expression of a truncated CryIA(b)     toxin. Bt11 maize also transgenically expresses the enzyme PAT to     achieve tolerance to the herbicide glufosinate ammonium. -   2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31     790 St. Sauveur, France, registration number C/FR/96/05/10.     Genetically modified Zea mays which has been rendered resistant to     attack by the European corn borer (Ostrinia nubilalis and Sesamia     nonagrioides) by transgenic expression of a CryIA(b) toxin. Bt176     maize also transgenically expresses the enzyme PAT to achieve     tolerance to the herbicide glufosinate ammonium. -   3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31     790 St. Sauveur, France, registration number C/FR/96/05/10. Maize     which has been rendered insect-resistant by transgenic expression of     a modified CryIIIA toxin. This toxin is Cry3A055 modified by     insertion of a cathepsin-D-protease recognition sequence. The     preparation of such transgenic maize plants is described in WO     03/018810. -   4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de     Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.     MON 863 expresses a CryIIIB(b1) toxin and has resistance to certain     Coleoptera insects. -   5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de     Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02. -   6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7     B-1160 Brussels, Belgium, registration number C/NL/00/10.     Genetically modified maize for the expression of the protein Cry1F     for achieving resistance to certain Lepidoptera insects and of the     PAT protein for achieving tolerance to the herbicide glufosinate     ammonium. -   7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de     Tervuren, B-1150 Brussels, Belgium, registration number     C/GB/02/M3/03. Consists of conventionally bred hybrid maize     varieties by crossing the genetically modified varieties NK603 and     MON 810. NK603×MON 810 Maize transgenically expresses the protein     CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts     tolerance to the herbicide Roundup® (contains glyphosate), and also     a CryIA(b) toxin obtained from Bacillus thuringiensis subsp.     kurstaki which brings about tolerance to certain Lepidoptera,     include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fur Biosicherheit and Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

The term “crops” is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called “plant disease resistance genes”, as described in WO 03/000906).

Further areas of use of the compounds according to the invention are the protection of stored goods and storerooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.

In the hygiene sector, the compounds according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

Examples of such parasites are:

-   Of the order Anoplurida: Haematopinus spp., Linognathus spp.,     Pediculus spp. and Phtirus spp., Solenopotes spp. -   Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton     spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina     spp., Trichodectes spp. and Felicola spp. -   Of the order Diptera and the suborders Nematocerina and     Brachycerina, for example Aedes spp., Anopheles spp., Culex spp.,     Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,     Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp.,     Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca     spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp.,     Fannia spp., Glossina spp., Calliphora spp., Lucilia spp.,     Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp.,     Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp.     and Melophagus spp. -   Of the order Siphonapterida, for example Pulex spp., Ctenocephalides     spp., Xenopsylla spp., Ceratophyllus spp. -   Of the order Heteropterida, for example Cimex spp., Triatoma spp.,     Rhodnius spp., Panstrongylus spp. -   Of the order Blattarida, for example Blatta orientalis, Periplaneta     americana, Blattelagermanica and Supella spp. -   Of the subclass Acaria (Acarida) and the orders Meta- and     Meso-stigmata, for example Argas spp., Ornithodorus spp., Otobius     spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,     Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus     spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and     Varroa spp., -   Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata),     for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp.,     Myobia spp., Psorergates spp., Demodex spp., Trombicula spp.,     Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp.,     Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp.,     Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp.,     Cytodites spp. and Laminosioptes spp.

The compounds according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.

The invention therefore also relates to pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise—at least—one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.

In these compositions, the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with—at least—one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C₈ to C₁₂ of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil, and silicone oils.

Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly disperse silicas or highly disperse absorbtive polymers. Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand. In addition, a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.

Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties. The surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.

Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups. Normally, the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates.

Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethyl-ammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds. Examples of suitable soaps are the alkali, alkaline earth or (unsubstituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates. However, synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. As a rule, the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 C atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate. Also possible are, furthermore, suitable phosphates, such as salts of the phosphoric ester of a p-nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.

As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid adjuvant, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants(% in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient. Preferred compositions are composed in particular as follows (%=percent by weight):

Emulsifiable concentrates: active ingredient:   1 to 95%, preferably 5 to 20% surfactant:   1 to 30%, preferably 10 to 20% solvent:   5 to 98%, preferably 70 to 85% Dusts: active ingredient:  0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspension concentrates: active ingredient:   5 to 75%, preferably 10 to 50% water:   94 to 24%, preferably 88 to 30% surfactant:   1 to 40%, preferably 2 to 30% Wettable powders: active ingredient:  0.5 to 90%, preferably 1 to 80% surfactant:  0.5 to 20%, preferably 1 to 15% solid carrier:   5 to 99%, preferably 15 to 98% Granulates: active ingredient:  0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%

The compositions can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.

The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring—which are to be selected to suit the intended aims of the prevailing circumstances—and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.

The compositions according to the invention are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compositions prior to planting, for example seed can be treated prior to sowing. Alternatively, the compositions can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention.

PREPARATION EXAMPLES

The examples which follow are intended to illustrate the invention and show preferred compounds of formula I. Free valences represent the methyl group.

Example P1 Preparation of Compound T1.1.49 Step 1: Preparation of 5-chloro-3-methyl-2-sulfinylaminobenzoyl chloride

In analogy to J. Garin et al., Tetrahedron Lett. 1991, 32, 3263-3264:

To a suspension of 2-amino-5-chloro-3-methyl-benzoic acid (18.5 g, 100 mmol) in toluene (200 ml) was added thionyl chloride (36 ml, 500 mmol) and the mixture was heated to reflux and stirred at that temperature until the rapid gas evolution slowed down. The resulting solution was concentrated under reduced pressure to give a solid residue which was dried under high vacuum. The crude solid product (23.7 g, 95%) was used in the next step without further purification.

¹H-NMR (CDCI₃): 8.07 (d, 1H), 7.56 (d, 1H), 2.30 (s, 3H).

Step 2: Preparation of 2-amino-2-cyclopropylpropionitrile

In analogy to J. L. Marco et al., Tetrahedron 1999, 55, 7625-7644:

A solution of cyclopropyl methyl ketone (17.1 g, 203 mmol) and 101.9 ml of a 2.12 M stock solution of NH₄Cl in H₂O (216 mmol) in 30.6 ml of 25% ammonium hydroxide (216 mmol) was cooled with an ice-bath. To the mixture was added KCN (14.1 g, 216 mmol) and the mixture was stirred at RT for 5 hours. The reaction mixture was diluted with ethyl acetate, the organic layer separated, the H₂O layer extracted with ethyl acetate and the combined organic layers washed with water, brine, dried (Na₂SO₄), filtered and concentrated. The crude oily product (13.08 g, 58%) was used in the next step without further purification.

¹H-NMR (CDCl₃): 1.86 (br s, 2H), 1.56 (s, 3H), 1.13-1.04 (m, 1H), 0.63-0.53 (m, 4H).

Step 3: Preparation of 2-amino-5-chloro-N-(cyano-cyclopropyl-methyl-methyl)-3-methyl-benzamide

To a solution of 2-amino-2-cyclopropylpropionitrile [the product of step 2] (408 mg, 3.7 mmol) and triethylamine (0.62 ml, 4.4 mmol) in tetrahydrofuran (6 ml) cooled at 0-5° C. was added a solution of 5-methyl-3-methyl-2-sulfinylaminobenzoyl chloride [the product of step 1] (925 mg, 3.7 mmol) in tetrahydrofuran (4 ml). The reaction mixture was stirred at room temperature for an hour, and then poured into water. After extraction with ethyl acetate, the combined organic layers were washed with brine, dried (Na₂SO₄), filtered and concentrated. The crude product was purified by column chromatography on silica gel (ethyl acetate/hexane 1:3) to afford the title benzamide [compound D9, template Va from table D] (554 mg, 54%) as a white solid with a melting point of 156-158° C.

¹H-NMR (CDCl₃): 7.17 (d, 1H), 7.14 (d, 1H), 6.19 (s, 1H), 5.5-3.0 (br s, 2H), 2.15 (s, 3H), 1.86 (s, 3H), 1.39-1.30 (m, 1H), 0.83-0.73 (m, 4H); MS (electrospray ES+): 278, 280 ((M+H)⁺).

Step 4: Preparation of compound T1.1.49 2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylic acid {4-chloro-2-[(cyano-cyclopropyl-methyl-methyl)-carbamoyl]-6-methyl-phenyl}-amide

To a solution of 2-amino-5-chloro-N-(cyano-cyclopropyl-methyl-methyl)-3-methyl-benzamide [the product of step 3] (83 mg, 0.3 mmol) in tetrahydrofuran (6 ml) cooled at 0-5° C. was added a solution of 2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl chloride [prepared according to WO 02/070483, example 5G] (93 mg, 0.3 mmol) in tetrahydrofuran (4 ml). The reaction mixture was stirred at room temperature overnight, and the solvent evaporated in vacuo. The crude product was purified by column chromatography on silica gel (gradient ethyl acetate/hexane 1:4→1:1) to afford the title bisamide compound T1.1.49 (119 mg, 72%) as a white solid with a melting point of 226-228° C.

¹H-NMR (CDCl₃): 9.98 (s, 1H), 8.42 (d, 1H), 7.86 (d, 1H), 7.74 (s, 1H), 7.40 (dd, 1H), 7.17 (d, 1H), 7.13 (d, 1H), 6.66 (s, 1H), 2.17 (s, 3H), 1.69 (s, 3H), 1.19-1.10 (m, 1H), 0.67-0.54 (m, 4H); MS (electrospray ES+): 551, 553 ((M+H)⁺).

The compounds listed in the following Table P can be prepared analogous to the procedures described above (m.p.=melting point in ° C.).

TABLE P Compounds of formula I: Cmpd Phys. No. Structure Data T2.1.49

m.p. 173-175 T1.1.51

m.p. 235-237 T1.1.50

m.p. 244-246 T1.1.53

m.p. 206-207 T1.1.52

m.p. 241-243 T1.1.49

m.p. 222-224 T1.1.49a (enantiomer A)

Rt: 14.97 min¹ T1.1.49b (enantiomer B)

Rt: 16.79 min¹ T1.1.55

LCMC: M⁺: 513 T1.1.106

LCMC: M⁺: 654 T1.1.105

LCMC: M⁺: 643 T1.1.109

LCMC: M⁺: 572 T1.1.108

LCMC: M⁺: 624 T1.1.107

LCMC: M⁺: 609 T1.1.111

LCMC: M⁺: 605 T1.1.120

m.p. 197-198 T1.1.126

m.p. 203-204 ¹Rt: Retention time: HPLC on chiral phase (ChiralpackR AS-H 5 μm, 250 × 20 mm), mobile phase: 90/10 CO₂/MeOH, flow rate: 60 ml/min, detection: UV 230 nm, 25° C., outlet pressure: 150 bar).

The examples which follow are intended to illustrate the invention and show further preferred compounds of formula I. They do not limit the invention. “Me” is the methyl group.

TABLE A Substituent designations for Tables 1 to 8: Line R₉₁ R₉₂ R₉₃ P A.1.1 Me Cl CF₃ C A.1.2 Me Cl Br C A.1.3 Me Cl Cl C A.1.4 Me Cl CF₂H C A.1.5 Me Cl OCH₂CF₃ C A.1.6 Me Cl OCF₃ C A.1.7 Me Cl OCH₃ C A.1.8 Me Cl CN C A.1.9 Me Br CF₃ C A.1.10 Me Br Br C A.1.11 Me Br Cl C A.1.12 Me Br CF₂H C A.1.13 Me Br OCH₂CF₃ C A.1.14 Me Br OCF₃ C A.1.15 Me Br OCH₃ C A.1.16 Me Br CN C A.1.17 Cl Cl CF₃ C A.1.18 Cl Cl Br C A.1.19 Cl Cl Cl C A.1.20 Cl Cl CF₂H C A.1.21 Cl Cl OCH₂CF₃ C A.1.22 Cl Cl OCF₃ C A.1.23 Cl Cl OCH₃ C A.1.24 Cl Cl CN C A.1.25 Cl Br CF₃ C A.1.26 Cl Br Br C A.1.27 Cl Br Cl C A.1.28 Cl Br CF₂H C A.1.29 Cl Br OCH₂CF₃ C A.1.30 Cl Br OCF₃ C A.1.31 Cl Br OCH₃ C A.1.32 Cl Br CN C A.1.33 Br Cl CF₃ C A.1.34 Br Cl Br C A.1.35 Br Cl Cl C A.1.36 Br Cl CF₂H C A.1.37 Br Cl OCH₂CF₃ C A.1.38 Br Cl OCF₃ C A.1.39 Br Cl OCH₃ C A.1.40 Br Cl CN C A.1.41 Br Br CF₃ C A.1.42 Br Br Br C A.1.43 Br Br Cl C A.1.44 Br Br CF₂H C A.1.45 Br Br OCH₂CF₃ C A.1.46 Br Br OCF₃ C A.1.47 Br Br OCH₃ C A.1.48 Br Br CN C A.1.49 Me Cl CF₃ N A.1.50 Me Cl Br N A.1.51 Me Cl Cl N A.1.52 Me Cl CF₂H N A.1.53 Me Cl OCH₂CF₃ N A.1.54 Me Cl OCF₃ N A.1.55 Me Cl OCH₃ N A.1.56 Me Cl CN N A.1.57 Me Br CF₃ N A.1.58 Me Br Br N A.1.59 Me Br Cl N A.1.60 Me Br CF₂H N A.1.61 Me Br OCH₂CF₃ N A.1.62 Me Br OCF₃ N A.1.63 Me Br OCH₃ N A.1.64 Me Br CN N A.1.65 Cl Cl CF₃ N A.1.66 Cl Cl Br N A.1.67 Cl Cl Cl N A.1.68 Cl Cl CF₂H N A.1.69 Cl Cl OCH₂CF₃ N A.1.70 Cl Cl OCF₃ N A.1.71 Cl Cl OCH₃ N A.1.72 Cl Cl CN N A.1.73 Cl Br CF₃ N A.1.74 Cl Br Br N A.1.75 Cl Br Cl N A.1.76 Cl Br CF₂H N A.1.77 Cl Br OCH₂CF₃ N A.1.78 Cl Br OCF₃ N A.1.79 Cl Br OCH₃ N A.1.80 Cl Br CN N A.1.81 Br Cl CF₃ N A.1.82 Br Cl Br N A.1.83 Br Cl Cl N A.1.84 Br Cl CF₂H N A.1.85 Br Cl OCH₂CF₃ N A.1.86 Br Cl OCF₃ N A.1.87 Br Cl OCH₃ N A.1.88 Br Cl CN N A.1.89 Br Br CF₃ N A.1.90 Br Br Br N A.1.91 Br Br Cl N A.1.92 Br Br CF₂H N A.1.93 Br Br OCH₂CF₃ N A.1.94 Br Br OCF₃ N A.1.95 Br Br OCH₃ N A.1.96 Br Br CN N A.1.97 Me I CF₃ C A.1.98 Me I Br C A.1.99 Me I Cl C A.1.100 Me I CF₂H C A.1.101 Me I OCH₂CF₃ C A.1.102 Me I OCF₃ C A.1.103 Me I OCH₃ C A.1.104 Me I CN C A.1.105 Me I CF₃ N A.1.106 Me I Br N A.1.107 Me I Cl N A.1.108 Me I CF₂H N A.1.109 Me I OCH₂CF₃ N A.1.110 Me I OCF₃ N A.1.111 Me I OCH₃ N A.1.112 Me I CN N A.1.113 Me Cl OCF₂H C A.1.114 Me Br OCF₂H C A.1.115 Cl Cl OCF₂H C A.1.116 Cl Br OCF₂H C A.1.117 Br Cl OCF₂H C A.1.118 Br Br OCF₂H C A.1.119 Me I OCF₂H C A.1.120 Me Cl OCF₂H N A.1.121 Me Br OCF₂H N A.1.122 Cl Cl OCF₂H N A.1.123 Cl Br OCF₂H N A.1.124 Br Cl OCF₂H N A.1.125 Br Br OCF₂H N A.1.126 Me I OCF₂H N

TABLE 1 This table discloses the 126 compounds T1.1.1 to T1.1.126 of the formula in which, for each of these 126 specific compounds, each of the variables R₉₁, R₉₂, R₉₃, and P has the specific meaning given in the corresponding line, appropriately selected from the 126 lines A.1.1 to A.1.126, of the Table A. (T1)

For example, the specific compound T1.1.23 is the compound of the formula T1, in which each of the of the variables R₉₁, R₉₂, R₉₃ and P has the specific meaning given in the line A.1.23 of the Table A. According to the same system, also all of the other 95 specific compounds disclosed in the Table 1 as well as all of the specific compounds disclosed in the Tables 2 to 8 are specified analogously.

TABLE 2 This table discloses the 126 compounds T2.1.1 to T2.1.126 of the formula in which, for each of these 126 specific compounds, each of the variables R₉₁, R₉₂, R₉₃, and P has the specific meaning given in the corresponding line, appropriately selected from the 126 lines A.1.1 to A.1.126, of the Table A. (T2)

TABLE 3 This table discloses the 126 compounds T3.1.1 to T3.1.126 of the formula in which, for each of these 126 specific compounds, each of the variables R₉₁, R₉₂, R₉₃, and P has the specific meaning given in the corresponding line, appropriately selected from the 126 lines A.1.1 to A.1.126, of the Table A. (T3)

TABLE 4 This table discloses the 126 compounds T4.1.1 to T4.1.126 of the formula in which, for each of these 126 specific compounds, each of the variables R₉₁, R₉₂, R₉₃, and P has the specific meaning given in the corresponding line, appropriately selected from the 126 lines A.1.1 to A.1.126, of the Table A. (T4)

TABLE 5 This table discloses the 126 compounds T5.1.1 to T5.1.126 of the formula in which, for each of these 126 specific compounds, each of the variables R₉₁, R₉₂, R₉₃, and P has the specific meaning given in the corresponding line, appropriately selected from the 126 lines A.1.1 to A.1.126, of the Table A. (T5)

TABLE 6 This table discloses the 126 compounds T6.1.1 to T6.1.126 of the formula in which, for each of these 126 specific compounds, each of the variables R₉₁, R₉₂, R₉₃, and P has the specific meaning given in the corresponding line, appropriately selected from the 126 lines A.1.1 to A.1.126, of the Table A. (T6)

TABLE 7 This table discloses the 126 compounds T7.1.1 to T7.1.126 of the formula in which, for each of these 126 specific compounds, each of the variables R₉₁, R₉₂, R₉₃, and P has the specific meaning given in the corresponding line, appropriately selected from the 126 lines A.1.1 to A.1.126, of the Table A. (T7)

TABLE 8 This table discloses the 126 compounds T8.1.1 to T8.1.126 of the formula in which, for each of these 126 specific compounds, each of the variables R₉₁, R₉₂, R₉₃, and P has the specific meaning given in the corresponding line, appropriately selected from the 126 lines A.1.1 to A.1.126, of the Table A. (T8)

Formulation Examples (%=percent by weight) Example F1

Emulsion concentrates a) b) c) Active ingredient 25% 40% 50% Calcium dodecylbenzenesulfonate  5%  8%  6% Castor oil polyethylene glycol ether  5% — — (36 mol of EO) Tributylphenoxypolyethylene glycol ether — 12%  4% (30 mol of EO) Cyclohexanone — 15% 20% Xylene mixture 65% 25% 20%

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

Example F2

Solutions a) b) c) d) Active ingredient 80% 10% 5% 95% Ethylene glycol monomethyl ether 20% — — — Polyethylene glycol MW 400 — 70% — — N-Methylpyrrolid-2-one — 20% — — Epoxidized coconut oil — — 1%  5% Petroleum ether (boiling range: 160-190°) — — 94%  —

The solutions are suitable for use in the form of microdrops.

Example F3

Granules a) b) c) d) Active ingredient 5% 10%  8% 21% Kaolin 94%  — 79% 54% Highly disperse silica 1% — 13%  7% Attapulgite — 90% — 18%

The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier(s), and the solvent is subsequently evaporated in vacuo.

Example F4

Dusts a) b) Active ingredient 2% 5% Highly disperse silica 1% 5% Talc 97%  — Kaolin — 90% 

Ready-to-use dusts are obtained by intimately mixing the carriers and the active ingredient.

Example F5

Wettable powders a) b) c) Active ingredient 25%  50% 75% Sodium lignosulfonate 5%  5% — Sodium lauryl sulfate 3% —  5% Sodium diisobutylnaphthalenesulfonate —  6% 10% Octylphenoxypolyethylene glycol —  2% — ether (7-8 mol of EO) Highly disperse silica 5% 10% 10% Kaolin 62%  27% —

The active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders, which can be diluted with water to give suspensions of any desired concentration.

Example F6

Extruder granules Active ingredient 10% Sodium lignosulfonate  2% Carboxymethylcellulose  1% Kaolin 87%

The active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.

Example F7

Coated granules Active ingredient 3% Polyethylene glycol (MW 200) 3% Kaolin 94% 

In a mixer, the finely ground active ingredient is applied uniformly to the kaolin, which has been moistened with the polyethylene glycol. This gives dust-free coated granules.

Example F8

Suspension concentrate Active ingredient 40% Ethylene glycol 10% Nonylphenoxypolyethylene glycol ether (15 mol of EO)  6% Sodium lignosulfonate 10% Carboxymethylcellulose  1% 37% aqueous formaldehyde solution 0.2%  Silicone oil (75% aqueous emulsion) 0.8%  Water 32%

The finely ground active ingredient is mixed intimately with the additives. Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.

The activity of the compounds according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally or acaricidally active ingredients. Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

The following mixtures of the compounds of formula I with active ingredients are preferred (the abbreviation “TX” means: “one compound selected from the group consisting of the compounds specifically described in Tables T1, T2, T3, T4, T5, T6, T7 and T8 of the present invention”):

an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628)+TX,

an acaricide selected from the group of substances consisting of 1,1-bis(4-chloro-phenyl)-2-ethoxyethanol (IUPAC name) (910)+TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name) (1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX, abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin (202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amidothioate (872)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, aramite (881)+TX, arsenous oxide (882)+TX, AVI 382 (compound code)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX, azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX, azocyclotin (46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos (alternative name) [CCN]+TX, benzoximate (71)+TX, benzyl benzoate (IUPAC name) [CCN]+TX, bifenazate (74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX, brofenvalerate (alternative name)+TX, bromocyclen (918)+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX, bromopropylate (94)+TX, buprofezin (99)+TX, butocarboxim (103)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX, calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbophenothion (947)+TX, CGA 50′439 (development code) (125)+TX, chinomethionat (126)+TX, chlorbenside (959)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX, chlorfenapyr (130)+TX, chlorfenethol (968)+TX, chlorfenson (970)+TX, chlorfensulphide (971)+TX, chlorfenvinphos (131)+TX, chlorobenzilate (975)+TX, chloromebuform (977)+TX, chloromethiuron (978)+TX, chloropropylate (983)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX, chlorthiophos (994)+TX, cinerin I (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, clofentezine (158)+TX, closantel (alternative name) [CCN]+TX, coumaphos (174)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb (1013)+TX, cyanthoate (1020)+TX, cyflumetofen (CAS Reg. No.: 400882-07-7)+TX, cyhalothrin (196)+TX, cyhexatin (199)+TX, cypermethrin (201)+TX, DCPM (1032)+TX, DDT (219)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon (227)+TX, dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos (alternative name)+TX, dicofol (242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX, dimefox (1081)+TX, dimethoate (262)+TX, dinactin (alternative name) (653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinobuton (269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6 [CCN]+TX, dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon (1097)+TX, dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone (IUPAC name) (1103)+TX, disulfiram (alternative name) [CCN]+TX, disulfoton (278)+TX, DNOC (282)+TX, dofenapyn (1113)+TX, doramectin (alternative name) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX, EPN (297)+TX, eprinomectin (alternative name) [CCN]+TX, ethion (309)+TX, ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX, fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX, fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX, fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil (1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX, fluacrypyrim (360)+TX, fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron (370)+TX, flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate (1184)+TX, FMC 1137 (development code) (1185)+TX, formetanate (405)+TX, formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX, heptenophos (432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstracts name) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPAC name) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX, jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX, malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan (1261)+TX, mesulfen (alternative name) [CCN]+TX, methacrifos (1266)+TX, methamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX, methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX, mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX, monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternative name) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512 (compound code)+TX, nifluridide (1309)+TX, nikkomycins (alternative name) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compound code)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT (219)+TX, parathion (615)+TX, permethrin (626)+TX, petroleum oils (alternative name) (628)+TX, phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon (639)+TX, phoxim (642)+TX, pirimiphos-methyl (652)+TX, polychloroterpenes (traditional name) (1347)+TX, polynactins (alternative name) (653)+TX, proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite (671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion (701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos (711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX, RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan (1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen (738)+TX, spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX, sulfiram (alternative name) [CCN]+TX, sulfluramid (750)+TX, sulfotep (753)+TX, sulfur (754)+TX, SZI-121 (development code) (757)+TX, tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam (alternative name)+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX, tetranactin (alternative name) (653)+TX, tetrasul (1425)+TX, thiafenox (alternative name)+TX, thiocarboxime (1431)+TX, thiofanox (800)+TX, thiometon (801)+TX, thioquinox (1436)+TX, thuringiensin (alternative name) [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX, trifenofos (1455)+TX, trinactin (alternative name) (653)+TX, vamidothion (847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX,

an algicide selected from the group of substances consisting of bethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, copper sulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen (232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX, nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine (730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX,

an anthelmintic selected from the group of substances consisting of abamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX, milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name) [CCN]+TX, spinosad (737) and thiophanate (1435)+TX,

an avicide selected from the group of substances consisting of chloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX,

a bactericide selected from the group of substances consisting of 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX, 8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copper dioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name) (169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione (1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde (404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin (483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin (580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline (611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole (658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX, tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,

a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12)+TX, Agrobacterium radiobacter (alternative name) (13) +TX, Amblyseius spp. (alternative name) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX, Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis (alternative name) (33)+TX, Aphidius colemani (alternative name) (34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographa californica NPV (alternative name) (38)+TX, Bacillus firmus (alternative name) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX, Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveria bassiana (alternative name) (53)+TX, Beauveria brongniartii (alternative name) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX, Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonella GV (alternative name) (191)+TX, Dacnusa sibirica (alternative name) (212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa (scientific name) (293)+TX, Eretmocerus eremicus (alternative name) (300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastix dactylopii (alternative name) (488)+TX, Macrolophus caliginosus (alternative name) (491)+TX, Mamestra brassicae NPV (alternative name) (494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhizium anisopliae var. acridum (scientific name) (523)+TX, Metarhizium anisopliae var. anisopliae (scientific name) (523)+TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp. (alternative name) (596)+TX, Paecilomyces fumosoroseus (alternative name) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741)+TX, Steinernema bibionis (alternative name) (742)+TX, Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae (alternative name) (742)+TX, Steinernema glaseri (alternative name) (742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernema riobravis (alternative name) (742)+TX, Steinernema scapterisci (alternative name) (742)+TX, Steinernema spp. (alternative name) (742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848)+TX,

a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537)+TX,

a chemosterilant selected from the group of substances consisting of apholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan (alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif (alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa [CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid [CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX, thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name) [CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN]+TX,

an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX, (E+TX, Z)-tetradeca-4+TX, 10-dien-1-yl acetate (IUPAC name) (779)+TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal (IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX, (Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX, (7E+TX, 9Z)-dodeca-7 +TX, 9-dien-1-yl acetate (IUPAC name) (283)+TX, (9Z +TX, 11E)-tetradeca-9+TX, 11-dien-1-yl acetate (IUPAC name) (780)+TX, (9Z+TX, 12E)-tetradeca-9+TX, 12-dien-1-yl acetate (IUPAC name) (781)+TX, 14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin (alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX, codlelure (alternative name) [CCN]+TX, codlemone (alternative name) (167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX, dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate (IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name) (284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl 4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name) [CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternative name) (420)+TX, grandlure (421)+TX, grandlure I (alternative name) (421)+TX, grandlure II (alternative name) (421)+TX, grandlure III (alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX, hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol (alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX, lineatin (alternative name) [CCN]+TX, litlure (alternative name) [CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX, megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternative name) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate (IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name) (589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternative name) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX, sordidin (alternative name) (736)+TX, sulcatol (alternative name) [CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure (839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B₁ (alternative name) (839)+TX, trimedlure B₂ (alternative name) (839)+TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN]+TX,

an insect repellent selected from the group of substances consisting of 2-(octylthio)-ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX, butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name) (1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX, dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide [CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX, oxamate [CCN] and picaridin [CCN]+TX,

an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX, 1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC/Chemical Abstracts name) (935)+TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/Chemical Abstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX, 2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX, acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX, allosamidin (alternative name) [CCN]+TX, allyxycarb (866)+TX, alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name) [CCN]+TX, aluminium phosphide (640)+TX, amidithion (870)+TX, amidothioate (872)+TX, aminocarb (873)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, anabasine (877)+TX, athidathion (883)+TX, AVI 382 (compound code)+TX, AZ 60541 (compound code)+TX, azadirachtin (alternative name) (41)+TX, azamethiphos (42)+TX, azinphos-ethyl (44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillus thuringiensis delta endotoxins (alternative name) (52)+TX, barium hexafluorosilicate (alternative name) [CCN]+TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer 22/190 (development code) (893)+TX, Bayer 22408 (development code) (894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX, beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX, bifenthrin (76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin (908)+TX, bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name) (909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenvalerate (alternative name)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX, bromo-DDT (alternative name) [CCN]+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX, butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate (932)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX, cadusafos (109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX, calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbon disulfide (IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride (IUPAC name) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX, cartap (123)+TX, cartap hydrochloride (123)+TX, cevadine (alternative name) (725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone (963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX, chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos (131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform [CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos (990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX, chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternative name)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX, cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX, clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate [CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate (1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos (1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS 708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos (184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin (188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin (201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate (alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX, d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet (216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX, dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon (1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos (alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos (243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl 5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron (250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX, dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin (1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam (1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan (1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion (1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX, doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone (alternative name) [CCN]+TX, El 1642 (development code) (1118)+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX, empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin (1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX, eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX, etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion (309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos (312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternative name) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride (chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX, etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos (326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenethacarb (1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb (336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin (1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX, fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX, flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX, flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX, flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code) (1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX, fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX, fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX, gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX, guazatine acetates (422)+TX, GY-81 (development code) (423)+TX, halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD (1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos [CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX, hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX, imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX, iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX, isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin (1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX, isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion (480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX, jodfenphos (1248)+TX, juvenile hormone I (alternative name) [CCN]+TX, juvenile hormone II (alternative name) [CCN]+TX, juvenile hormone III (alternative name) [CCN]+TX, kelevan (1249)+TX, kinoprene (484)+TX, lambda-cyhalothrin (198)+TX, lead arsenate [CCN]+TX, lepimectin (CCN)+TX, leptophos (1250)+TX, lindane (430)+TX, lirimfos (1251)+TX, lufenuron (490)+TX, lythidathion (1253)+TX, m-cumenyl methylcarbamate (IUPAC name) (1014)+TX, magnesium phosphide (IUPAC name) (640)+TX, malathion (492)+TX, malonoben (1254)+TX, mazidox (1255)+TX, mecarbam (502)+TX, mecarphon (1258)+TX, menazon (1260)+TX, mephosfolan (1261)+TX, mercurous chloride (513)+TX, mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metam (519)+TX, metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX, methacrifos (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride (IUPAC/Chemical Abstracts name) (1268)+TX, methidathion (529)+TX, methiocarb (530)+TX, methocrotophos (1273)+TX, methomyl (531)+TX, methoprene (532)+TX, methoquin-butyl (1276)+TX, methothrin (alternative name) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methyl bromide (537)+TX, methyl isothiocyanate (543)+TX, methylchloroform (alternative name) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin [CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX, monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternative name) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX, naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170 (development code) (1306)+TX, NC-184 (compound code)+TX, nicotine (578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram (579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron (585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name) (1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (IUPAC name) (1075)+TX, O,O,O′,O′-tetrapropyl dithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name) (593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl (609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp'-DDT (219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX, parathion-methyl (616)+TX, penfluron (alternative name) [CCN]+TX, pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name) (623)+TX, permethrin (626)+TX, petroleum oils (alternative name) (628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX, phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX, phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX, phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX, pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX, polychloroterpenes (traditional name) (1347)+TX, potassium arsenite [CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX, precocene I (alternative name) [CCN]+TX, precocene II (alternative name) [CCN]+TX, precocene IIl (alternative name) [CCN]+TX, primidophos (1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl (1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos (686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine (688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin (1367)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion (701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen (708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX, quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX, rafoxanide (alternative name) [CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (development code) (723)+TX, RU 25475 (development code) (1386)+TX, ryania (alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX, sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009 (compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compound code)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129 (development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX, sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide (623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate [CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX, spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX, sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX, sulprofos (1408)+TX, tar oils (alternative name) (758)+TX, tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX, tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX, teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP (1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX, terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos (777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX, thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam (792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam (798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX, thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap (803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name) [CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin (813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate (818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX, trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX, trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX, vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine (alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302 (compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternative name)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901 (development code) (858)+TX,

a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX, calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite [CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate (IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX, niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol (623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX,

a nematicide selected from the group of substances consisting of AKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX, 1,3-dichloropropene (233)+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX, abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz [CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX, cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide (945)+TX, carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos (145)+TX, cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX, dazomet (216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX, dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate (262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX, ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX, fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate (408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX, GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane (IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX, ivermectin (alternative name) [CCN]+TX, kinetin (alternative name) (210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide (537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrothecium verrucaria composition (alternative name) (565)+TX, NC-184 (compound code)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX, phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternative name)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/Chemical Abstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin (1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name) (210)+TX,

a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,

a plant activator selected from the group of substances consisting of acibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720)+TX,

a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX, alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu (880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX, bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX, bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX, chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX, coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX, crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX, diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX, fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadine hydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogen cyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX, magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX, norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name) (640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite [CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX, strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zinc phosphide (640)+TX,

a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)-ethyl piperonylate (IUPAC name) (934)+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX, farnesol with nerolidol (alternative name) (324)+TX, MB-599 (development code) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide (649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (development code) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide (1406)+TX,

an animal repellent selected from the group of substances consisting of anthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX, copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene (chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates (422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX, thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram (856)+TX,

a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX,

a wound protectant selected from the group of substances consisting of mercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl (802)+TX,

an insecticide selected from the group consisting of the compound of formula A-1

and biologically active compounds selected from the group consisting of Azaconazole (60207-31-0]+TX, Bitertanol [70585-36-3]+TX, Bromuconazole [116255-48-2]+TX, Cyproconazole [94361-06-5]+TX, Difenoconazole [119446-68-3]+TX, Diniconazole [83657-24-3]+TX, Epoxiconazole [106325-08-0]+TX, Fenbuconazole [114369-43-6]TX, Fluquinconazole [136426-54-5]+TX, Flusilazole [85509-19-9]+TX, Flutriafol [76674-21-0]+TX, Hexaconazole [79983-71-4]+TX, Imazalil [35554-44-0]+TX Imibenconazole [86598-92-7]+TX, Ipconazole [125225-28-7]+TX, Metconazole [125116-23-6]+TX, Myclobutanil [88671-89-0]+TX, Pefurazoate [101903-30-4]+TX, Penconazole [66246-88-6]+TX, Prothioconazole [178928-70-6]+TX, Pyrifenox [88283-41-4]+TX, Prochloraz [67747-09-5]+TX, Propiconazole [60207-90-1]+TX, Simeconazole [149508-90-7]+TX, Tebuconazole [107534-96-3]+TX, Tetraconazole [112281-77-3]+TX, Triadimefon [43121-43-3]+TX, Triadimenol [55219-65-3]+TX, Triflumizole [99387-89-0]+TX, Triticonazole [131983-72-7]+TX, Ancymidol [12771-68-5]+TX, Fenarimol [60168-88-9]+TX, Nuarimol [63284-71-9]+TX, Bupirimate [41483-43-6]+TX, Dimethirimol [5221-53-4]+TX, Ethirimol [23947-60-6]+TX, Dodemorph [1593-77-7]+TX, Fenpropidine [67306-00-7]+TX, Fenpropimorph [67564-91-4]+TX, Spiroxamine [118134-30-8]+TX, Tridemorph [81412-43-3]+TX, Cyprodinil [121552-61-2]+TX, Mepanipyrim [110235-47-7]+TX, Pyrimethanil [53112-28-0]+TX, Fenpiclonil [74738-17-3]+TX, Fludioxonil [131341-86-1]+TX, Benalaxyl [71626-11-4]+TX, Furalaxyl [57646-30-7]+TX, Metalaxyl [57837-19-1]+TX, R-Metalaxyl [70630-17-0]+TX, Ofurace [58810-48-3]+TX, Oxadixyl [77732-09-3]+TX, Benomyl [17804-35-2]+TX, Carbendazim [10605-21-7]+TX, Debacarb [62732-91-6]+TX, Fuberidazole [3878-19-1]+TX, Thiabendazole [148-79-8]+TX, Chlozolinate [84332-86-5]+TX, Dichlozoline [24201-58-9]+TX, Iprodione [36734-19-7]+TX, Myclozoline [54864-61-8]+TX, Procymidone [32809-16-8]+TX, Vinclozoline [50471-44-8]+TX, Boscalid [188425-85-6]+TX, Carboxin [5234-68-4]+TX, Fenfuram [24691-80-3]+TX, Flutolanil [66332-96-5]+TX, Mepronil [55814-41-0]+TX, Oxycarboxin [5259-88-1]+TX, Penthiopyrad [183675-82-3]+TX, Thifluzamide [130000-40-7]+TX, Guazatine [108173-90-6]+TX, Dodine [2439-10-3][112-65-2] (freie Base)+TX, Iminoctadine [13516-27-3]+TX, Azoxystrobin [131860-33-8]+TX, Dimoxystrobin [149961-52-4]+TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93}+TX, Fluoxastrobin [361377-29-9]+TX, Kresoxim-methyl [143390-89-0]+TX, Metominostrobin [133408-50-1]+TX, Trifloxystrobin [141517-21-7]+TX, Orysastrobin [248593-16-0]+TX, Picoxystrobin [117428-22-5]+TX, Pyraclostrobin [175013-18-0]+TX, Ferbam [14484-64-1]+TX, Mancozeb [8018-01-7]+TX, Maneb [12427-38-2]+TX, Metiram [9006-42-2]+TX, Propineb [12071-83-9]+TX, Thiram [137-26-8]+TX, Zineb [12122-67-7]+TX, Ziram [137-30-4]+TX, Captafol [2425-06-1]+TX, Captan [133-06-2]+TX, Dichlofluanid [1085-98-9]+TX, Fluoroimide [41205-21-4]+TX, Folpet [133-07-3 ]+TX, Tolylfluanid [731-27-1]+TX, Bordeaux Mixture [8011-63-0]+TX, Copperhydroxid [20427-59-2]+TX, Copperoxychlorid [1332-40-7]+TX, Coppersulfat [7758-98-7]+TX, Copperoxid [1317-39-1]+TX, Mancopper [53988-93-5]+TX, Oxine-copper [10380-28-6]+TX, Dinocap [131-72-6]+TX, Nitrothal-isopropyl [10552-74-6]+TX, Edifenphos [17109-49-8]+TX, Iprobenphos [26087-47-8]+TX, Isoprothiolane [50512-35-1]+TX, Phosdiphen [36519-00-3]+TX, Pyrazophos [13457-18-6]+TX, Tolclofos-methyl [57018-04-9]+TX, Acibenzolar-S-methyl [135158-54-2]+TX, Anilazine [101-05-3]+TX, Benthiavalicarb [413615-35-7]+TX, Blasticidin-S [2079-00-7]+TX, Chinomethionat [2439-01-2]+TX, Chloroneb [2675-77-6]+TX, Chlorothalonil [1897-45-6]+TX, Cyflufenamid [180409-60-3]+TX, Cymoxanil [57966-95-7]+TX, Dichlone [117-80-6]+TX, Diclocymet [139920-32-4]+TX, Diclomezine [62865-36-5]+TX, Dicloran [99-30-9]+TX, Diethofencarb [87130-20-9]+TX, Dimethomorph [110488-70-5]+TX, SYP-LI90 (Flumorph) [211867-47-9]+TX, Dithianon [3347-22-6]+TX, Ethaboxam [162650-77-3]+TX, Etridiazole [2593-15-9]+TX, Famoxadone [131807-57-3]+TX, Fenamidone [161326-34-7]+TX, Fenoxanil [115852-48-7]+TX, Fentin [668-34-8]+TX, Ferimzone [89269-64-7]+TX, Fluazinam [79622-59-6]+TX, Fluopicolide [239110-15-7]+TX, Flusulfamide [106917-52-6]+TX, Fenhexamid [126833-17-8]+TX, Fosetyl-aluminium [39148-24-8]+TX, Hymexazol [10004-44-1]+TX, Iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid) [120116-88-3]+TX, Kasugamycin [6980-18-3]+TX, Methasulfocarb [66952-49-6]+TX, Metrafenone [220899-03-6]+TX, Pencycuron [66063-05-6]+TX, Phthalide [27355-22-2]+TX, Polyoxins [11113-80-7]+TX, Probenazole [27605-76-1]+TX, Propamocarb [25606-41-1]+TX, Proquinazid [189278-12-4]+TX, Pyroquilon [57369-32-1]+TX, Quinoxyfen [124495-18-7]+TX, Quintozene [82-68-8]+TX, Schwefel [7704-34-9]+TX, Tiadinil [223580-51-6]+TX, Triazoxide [72459-58-6]+TX, Tricyclazole [41814-78-2]+TX, Triforine [26644-46-2]+TX, Validamycin [37248-47-8]+TX, Zoxamide (RH7281) [156052-68-5]+TX, Mandipropamid [374726-62-2]+TX, the compound of formula F-1

wherein Ra₅ is trifluoromethyl or difluoromethyl (WO2004/058723)+TX, the compound of formula F-2

wherein Ra₆ is trifluoromethyl or difluoromethyl (WO2004/058723)+TX, the racemic compound of formula F-3 (syn)

wherein Ra₇ is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, the racemic mixture of formula F-4 (anti)

wherein Ra₇ is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, the compound of formula F-5

which is an epimeric mixture of racemic compounds of formulae F-3 (syn) and F-4 (anti), wherein the ratio from racemic compounds of formula F-3 (syn) to racemic cmpounds of formula F-4 (anti) is from 1000:1 to 1:1000 and wherein Ra, is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, the compound of formula F-6

wherein Ra₈ is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, the racemic compound of formula F-7 (trans)

wherein Ra₉ is trifluoromethyl or difluoromethyl (WO03/074491)+TX, the racemic compound of formula F-8 (cis)

wherein Ra₉ is trifluoromethyl or difluoromethyl (WO03/074491)+TX, the compound of formula F-9

which is a mixture of the racemic compounds of formulae F-7 (trans) and F-8 (cis), wherein the ratio of the racemic compound of formula F-7 (trans) to the racemic compound of formula F-8 (cis) is 2:1 to 100:1; and wherein Ra₉ is trifluoromethyl or difluoromethyl (WO03/074491)+TX,

-   -   the compound of formula F-10

wherein R₁₀ is trifluoromethyl or difluoromethyl (WO2004/058723)+TX, the racemic compound of formula F-11 (trans)

wherein R₁₁ is trifluoromethyl or difluoromethyl (WO03/074491)+TX, the racemic compound of formula F-12 (cis)

wherein R₁₁ is trifluoromethyl or difluoromethyl (WO03/074491)+TX, the compound of formula F-13

which is a racemic mixture of formulae F-11 (trans) and F-12 (cis), and wherein R₁₁ is trifluoromethyl or difluoromethyl (WO 03/074491)+TX, the compound of formula F-14

(WO2004/058723)+TX, and the compound of formula F-15

[214706-53-3], +TX.

The active ingredient mixture of the compounds of formula I selected from tables T1 to T8 with active ingredients described above comprises a compound selected from tables T1 to T8 and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 and 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:300, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.

The mixtures comprising a compound of formula I selected from tables T1 to T8 and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I selected from tables T1 to T8 and the active ingredients as described above is not essential for working the present invention.

The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The compouds of formulae A-1 to A-26 are described in WO 03/015518 or in WO 04/067528. The above described mixing partners are known. Where the active ingredients are included in “The Pesticide Manual” [The Pesticide Manual—A World Compendium; Thirteenth Edition; Editor: C. D. S. Tomlin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound “abamectin” is described under entry number (1). Where “[CCN]” is added hereinabove to the particular compound, the compound in question is included in the “Compendium of Pesticide Common Names”, which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound “acetoprole” is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred to hereinabove by a so-called “common name”, the relevant “ISO common name” or another “common name” being used in individual cases. If the designation is not a “common name”, the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemical name”, a “traditional name”, a “compound name” or a “develoment code” is used or, if neither one of those designations nor a “common name” is used, an “alternative name” is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.

Biological Examples %=Per Cent by Weight, Unless Otherwise Specified Example B1 Activity Against Spodoptera littoralis (Egyptian Cotton Leafworm):

Cotton leaf discs are placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs are infested with 5 L₁ larvae. The samples are checked for mortality, repellent effect, feeding behaviour, and growth inhibition 3 days after treatment (DAT).

In this test, compounds listed in Table P above show good activity. In particular compounds T1.1.53, T1.1.50, T1.1.52, T1.1.51, T1.1.49 and T2.1.49, T1.1.49a, T1.1.49b, T1.1.55, T.1.1.106, T.1.1.105, T.1.1.108, T.1.1.107 and T.1.1.11 provide over 80% mortality at 200 ppm.

Example B2 Activity Against Heliothis virescens (Tobacco Budworm)

Eggs (0-24 h old) are placed in 24-well microtiter plate on artificial diet and sprayed with test solutions. After an incubation period of 4 days, samples are checked for egg mortality, larval mortality, and growth inhibition.

In this test, compounds listed in Table P above show good activity. In particular compounds T1.1.53, T1.1.50, T1.1.52, T1.1.51, T1.1.49 and T2.1.49, T2.1.49, T1.1.49a, T1.1.49b, T1.1.55, T.1.1.106, T.1.1.105, T.1.1.108, T.1.1.107 and T.1.1.11 provide over 80% mortality at 200 ppm.

Example B3 Activity Against Plutella xvlostella (Diamond Back Moth)

24-well microtiter plate (MTP) with artificial diet is sprayed with test solutions. After drying, the MTP's are infested with larvae (L2)(10-15 per well). After an incubation period of 5 days, samples are checked for larval mortality, antifeedant and growth inhibition.

In this test, compounds listed in Table P above show good activity. In particular compounds T1.1.53, T1.1.50, T1.1.52, T1.1.51, T1.1.49 and T2.1.49, T2.1.49, T1.1.49a, T1.1.49b, T1.1.55, T.1.1.106, T.1.1.105, T.1.1.108, T.1.1.107 and T.1.1.11 provide over 80% mortality at 200 ppm.

Example B4 Activity Against Diabrotica balteata (Corn Root Worm)

24-well microtiter plate (MTP) with artificial diet is sprayed with test solutions. After drying, the MTP's are infested with larvae (L2)(6-10 per well). After an incubation period of 5 days, samples are checked for larval mortality, antifeedant and growth inhibition.

In this test, compounds listed in Table P above show good activity. In particular compounds T1.1.53, T1.1.50, T1.1.52, T1.1.51, T1.1.49 and T2.1.49, T2.1.49, T1.1.55, T.1.1.106, T.1.1.105 and T.1.1.108 provide over 80% at 200 ppm.

Example B5 Activity Against Mvzus persicae (Green Peach Aphid): (Contact)

Sunflower leaf discs are placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs are infested with an aphid population of mixed ages. After an incubation period of 6 DAT, samples are checked for mortality and special effects (e.g. phytotoxicity).

In this test, compounds listed in Table P above show good activity. In particular compounds T1.1.52 and T1.1.49 and T.1.1.105 provide over 80% mortality at 200 ppm.

Example B6 Activity Against Myzus persicae (Green Peach Aphid): (Systemic)

Roots of pea seedlings, infested with an aphid population of mixed ages, are placed directly in the test solutions. 6 days after introduction, samples are checked for mortality and special effects on the plant.

In this test, compounds listed in Table P above show good activity. In particular compounds T1.1.50, T1.1.52 and T2.1.49, T2.1.49 and T1.1.55 provide over 80% mortality at 12.5 ppm.

Example B7 Activity Against Thrips tabaci (Onion Thrips)

Sunflower leaf discs are placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs are infested with a thrips population of mixed ages. After an incubation period of 6 days, samples are checked for mortality and special effects (e.g. phytotoxicity).

In this test, compounds listed in Table P above show good activity. In particular compounds T1.1.50, T1.1.52, T1.1.51 and T1.1.49, T1.1.49.a, T1.1.49.b, T.1.1.105, T.1.1.108 and T.1.1.107 provide over 80% mortality at 200 ppm.

Example B8 Activity Against Tetranychus urticae (Two-Spotted Spider Mite)

Bean leaf discs on agar in 24-well microtiter plates are sprayed with test solutions. After drying, the leaf discs are infested with mite populations of mixed ages. 8 days later, discs are checked for egg mortality, larval mortality, and adult mortality.

In this test, compound T.1.1.107 above shows good activity (provides 80% mortality at 200 ppm).

Example B9 Systemic Insecticide Test for Spodoptera littoralis (Cotton Leafworm):

Four day old maize seedlings (Zea mais, variety Stoneville) are placed individual in vials containing 24 ml water into which the chemical is diluted at 12.5 ppm. Seedlings are allowed to grow for six days. Subsequently leaves are cut and placed in a Petri dish (5 cm diameter), inoculated with twelve to fifteen 1st instar S. littoralis larvae and incubated for four days in a growth chamber (25° C., 50% r.h., 18:6 L:D photo period). Number of alive insects are counted and percentage of dead calculated. Tests were conducted with one replicate.

In this test, compounds listed in Table P above show good activity. In particular compound T1.1.49, T1.1.50, T1.1.51, T1.1.52, T1.1.53, T1.1.55, T1.1.105, T1.1.106, T1.1.107, T1.1.11, T1.1.49.a and T1.1.49b provide over 80% mortality.

Example B10 Activity Against Cydia pomonella (Codling Moth)

Standard Cydia diet cubes (1.5 cm width) are pierced with a tooth-pick and are immersed in liquid paraffin (ca. 80° C.). After the paraffin coat has hardened, an aqueous emulsion containing 12.5 ppm of active ingredient is applied using a De Vilbis sprayer (25 ml, 1 bar). After the spray coating has dried, the cubes are put into plastic containers which are then populated with two freshly hatched Cydia pomonella (1^(st) instar). The containers are then closed with a plastic cap. After 14 days incubation at 26° C. and 40-60% relative humidity, the survival rate of the caterpillars as well as their growth regulation is determined.

In this test, compounds listed in Table P above show good activity. In particular compounds T1.1.49, T1.1.50, T1.1.51, T1.1.52, T1.1.53, T1.1.105, T1.1.107, T1.1.49.a and T1.1.49.b provide over 80% mortality.

Example B11 to B12 Comparison of the Insecticidal Activity of Compounds According to the Invention with the Structurally Most Closely Comparable Compound from the Prior Art (Compound No. A.1.346 Described on Page 76 of WO2006/040113)

Example B11 Systemic Insecticide Test for Spodoptera littoralis (Cotton Leafworm)

Four day old maize seedlings (Zea mais, variety Stoneville) are placed individual in vials containing 24 ml water into which the chemical is diluted at different concentrations. Seedlings are allowed to grow for six days. Subsequently leaves are cut and placed in a Petri dish (5 cm diameter), inoculated with twelve to fifteen 1st instar S. littoralis larvae and incubated for four days in a growth chamber (25° C., 50% r.h., 18:6 L:D photo period). Number of alive insects are counted and percentage of dead calculated.

Results are shown in Table B11:

TABLE B11 Systemic Activity Insecticide against Spodoptera littoralis Concentration Mortality (%) Compound: (ppm) after 5 days Comp. A.1.346 (state of the art) 0.05 100 Comp. A.1.346 (state of the art) 0.0125 0 Comp. T.1.1.49 (invention) 0.05 100 Comp. T.1.1.49 (invention) 0.0125 93

Table B11 shows that compound No. T.1.1.49 according to the invention exerts a substantially better insecticidal action on Spodoptera littoralis than the compound from the state of the art. Especially at the low application rate (0.0125 ppm) the compound according to the invention is far superior to the compound of the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds.

Example B12 Activity Against Frankliniella occidentalis (Western Flower Thrips)

Bean plants are treated in a spray chamber with diluted test solutions. After drying they are infested with mixed population. 12 days after the infestation, samples are checked for reduction of treated population and compared to the non treated population. Results are shown in Table B12:

TABLE B12 Activity Activity against Frankliniella occidentalis: Concentration Activity (%) Compound: (ppm) after 12 days Comp. A.1.346 (state of the art) 50 0 Comp. A.1.346 (state of the art) 25 0 Comp. A.1.346 (state of the art) 12.5 0 Comp. T.1.1.49 (invention) 50 90 Comp. T.1.1.49 (invention) 25 85 Comp. T.1.1.49 (invention) 12.5 75

Table B12 shows that compound No. T.1.1.49 according to the invention exerts a substantially better insecticidal action on Frankliniella occidentalis than the compound from the state of the art. At all application rates (50, 25 and 12.5 ppm) the compound according to the invention is far superior to the compound of the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds. 

1. A compound of the formula I

wherein D is phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl; or phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl mono-, di- or trisubstituted by C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, cyano, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl; or D is a group

R_(4a), R_(4b), R₁₀, R₁₇, and R₁₉ independently from each other, are hydrogen, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, cyano, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₂-C₄alkoxycarbonyl, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl; R_(5a), R₆, R₈, R₁₁, R₁₂, R₁₅, R₁₆ and R₁₈ independently from each other, are C₁-C₆alkyl, or C₁-C₆alkyl mono-, di- or trisubstituted by substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, C₁-C₄alkoxy, C₂-C₄alkoxycarbonyl, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₄dialkylamino and C₃-C₆cycloalkylamino; or are phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl; or are phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl mono-, di- or trisubstituted by substituents independently selected from the group consisting of C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, cyano, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfinyl and C₁-C₄haloalkylsulfonyl; R₇, R₉, R₁₃ and R₁₄ independently from each other, are hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₃-C₆alkynyl or C₃-C₆haloalkynyl; each R₁ independently is halogen, nitro, hydroxy, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino, C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy or C₃-C₆trialkylsilyl, phenyl, benzyl or phenoxy, or phenyl, benzyl or phenoxy mono-, di- or trisubstituted by halogen, cyano, nitro, halogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino, C₁-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy or C₃-C₆trialkylsilyl; n is 0, 1, 2 or 3; each of R₂ and R₃, which may be the same or different, represents hydrogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₈cycloalkyl; or C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₂-C₆alkynyl or C₃-C₈cycloalkyl substituted by one, two or three substituents independently selected from the group consisting of halogen nitro, cyano, hydroxy, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄haloalkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino and C₁-C₆alkyl-C₃-C₆cycloalkylamino; each of E₁ and E₂, which may be the same or different, represents oxygen or sulfur; G is a group

R₄ is C₁-C₃alkyl or C₃-C₄cycloalkyl; or C₁-C₃alkyl or C₃-C₄cycloalkyl substituted by one, two or three substituents independently selected from the group consisting of halogen, cyano, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₂-C₄alkoxycarbonyl and C₂-C₄haloalkoxycarbonyl; R₅ is C₃-C₄cycloalkyl or C₃-C₄cycloalkyl-C₁-C₃alkyl; or C₃-C₄cycloalkyl or C₃-C₄cycloalkyl-C₁-C₃alkyl substituted by one, two or three substituents independently selected from the group consisting of halogen, cyano, C₁-C₃alkyl, C₃-C₄cycloalkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₂-C₄alkoxycarbonyl and C₂-C₄haloalkoxycarbonyl; and agronomically acceptable salts/isomers/diastereomers/enantiomers/tautomers/N-oxides of those compounds.
 2. A process for the preparation of a compound of formula Vc

wherein G, n, R₁, R₃, E₂, R₄, and R₅ have the meanings given under formula I in claim 1 and X₁ is a leaving group, or, where appropriate, a tautomer and/or salt thereof, which process comprises reacting a compound of formula XI

wherein G, n, R₁ and E₂ have the meanings given under formula I in claim 1 and X₁ is a leaving group, with a compound of formula III

wherein R₁, R₄ and R₅ have the meanings given under formula I in claim 1, in the presence of a base and an inert solvent.
 3. A compound of formula V

in which G, n, R₁, R₂, R₃, E₂, R₄ and R₅ have the meanings given for formula I in claim
 1. 4. A pesticidal composition, which comprises at least one compound according to claim 1 of the formula I or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilizable salt form, as active ingredient and at least one auxiliary.
 5. A composition according to claim 4 for controlling insects or representatives of the order Acarina.
 6. A method for controlling pests, which comprises applying a composition according to claim 3 to the pests or their environment.
 7. A method according to claim 6 for controlling insects or representatives of the order Acarina.
 8. A method according to claim 6 for the protection of plant propagation material from the attack by pests, which comprises treating the propagation material or the site, where the propagation material is planted.
 9. Plant propagation material treated in accordance with the method described in claim
 8. 